Animalizing cellulosic fibers



Patented Nov. 3, 1942 UNITED STATES PATENTQOFFICE 2,300,589 snnuamzmcCELLULOSIC mans Johannes Nelles, Leverkusen-Schlebusch, and tto Bayer,Leverkusen I. G.-Werk, Germany, assignors, by mesne assignments, toGeneral Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application August 15, 1939, SerialNo. 290,220. In Germany August 23, 1938 Claims. (01. 106-164) especiallynitrogen, the high molecular character of which is caused by thepresence of high molecular aliphatic radicals or by condensation orpolymerization of low molecular basic compounds. It is also known thatanimalizing agents should be insoluble or difiicultly soluble in water,in order not to be removed from the fibers by wet treatments. In view oftheir insolubility in water and aqeuous liquids, animalizing agents werehitherto applied to the fibers or added to spinning solutions oi!artificial fibers in the form of solutions in organic solvents or in theform of aqueous dispersions.

We have now found an improvement in the art of animalizing whichconsists in employing. such v animalizing agents which, due to thepresence of at least one sulfonamido group in their molecule, aresoluble in alkali lyes. With the aid of these new animalizing agents itis now possible, for instance, to manufacture artificial fibers fromviscose spinning solutions containing the animalizing agenthomogeneously dissolved therein. Thereby the production of animalizedartificial fibers is very much simplified because it is no longernecessary to prepare special solutions or dispersions of the animalizingagent and to apply such solutions or dispersions in special workingsteps to the material; also the disturbances are avoided which oftenoccurred by. obstruction of pipes or nozzles of the spinning apparatus,when dispersions of an animalizing agent were added to the spinningsolution. Furthermore, an animalizing agent which is soluble in thespinning solution, can be more easily and homogeneously distributedthroughout the fiber than a pulverized and dispersed insoluble agent.

The animalizing agents to be used according to our invention may be ofvarious chemical structure. What they have in common are (1) the commbncharacteristics of all animalizing agents, 1. e. they are highmolecular, water insol uble basic substances, which increase the amnityof cellulosic fiber treated therewith to acid wool dyestuffs; and (2)theycontain one or more sulfonamldo groups by which they are renderedsoluble in alkali lyes, for instance, in caustic soda lye. As suchanimalizing agents there may be mentioned, for examplareaction productsfrom. aliphatic polyamines with arylsulioethyleneimides reactionproducts of chloroparaifinesuliochlorides obtainable according to the U.S. Patent No. 2,046,090, with ammonia or ethylenediamine, condensationproducts of benezylchloridep-sulfochloride with 111- and polyamines,condensation products of naphthaleneanddiphenyl-poly-(fl-chloroethylsulfamide) .with amines, reaction products.of polystyrene'sulfochlo-- ride with asymmetric dialkylethylenediamine,the formaldehyde condensation products of naphthalene-tri (asdiethylethylenediaminesuliamide) and many others.

Our invention is furthermore illustrated by the following examples, theparts being by weight, if not otherwise stated:

Example 1 7.5% of a reaction product from polyethyleneimine andbenzenesulioethyleneimide, (prepared ccording to Example 10 of the U. S.Patent No. 233,296 of Nelles et al. issued February 25, 1941) calculatedon the weight of the cellulose, are dissolved in a small quantity ofcaustic sodalye and stirred into a viscose spinning solution. Thesolution is then worked up into viscose staple fibers as usual.The'fibers so obtained have good afiinity for acid wool dyestuffs andmay be dyed alone or mixed with wool fibers, for instance, withSupranolbrillantred B (compare Schultz, Dyestufl Tables, vol. 2, 1932,p. 204), Anthralaneblue' G (compare 1. c., lrst supplemental vol., 1934,p. 68), 'piamondblack P23 (compare 1. 6., vol 1, 1931, p. 104). dyeingsoi! good fastness to wet obtained. 0

Example 2 treatments are To a reaction product according to Example 10tillation of the solvent, a tough, nearly colorless resin is obtainedwhich, by dissolving in dilute aqueous alkali, filtering andprecipitating with Very level dilute acetic acid, can be freed fromsmall quantities oi alkali-insoluble products.

12% of this alkali-soluble animalizing agent are added to a viscosespinning solution which.

is worked up as usual. The fibers so obtained ar dyed, alone or inmixture with animal fibers, by acid wool dyestuffs in very fast shades.

Example 3 Parafilne is treated with sulfur dioxide and chlorineaccording to the method described in U. 8. Patent No. 2,046,090, until.the chlorine content of the resulting product is about 38%. 300 parts ofthis product are heatedfor hours to 115-120 C.- with 270 partsethylenediamine (78%) in 150 parts butyl alcohol, similarly as describedin the French Patent No. 709,626.

7% of the resulting animalizing agent, calculated on the weight of thecellulose, dissolved in aqueous alkali are' incorporated with a viscosestaple fiber spinning solution. Fibers obtained therefrom are well dyedby acid wool dyestufls.

Example 4 p-Aminobenzenesuli'oethyleneimide (melting point 129-130 C.)is prepared according to Gabriel, Ber. d. deutsch. chem. Ges. 28. Pa e2933 by reactingp-acetylaminobenzenesuliochloride with ethyieneimine andsaponiiying with aqueous alkali. By heating the imide for several hoursto 100 C., a polymeric, infusible, colorless polyamide is obtained whichis soluble in dilute aqueous alkali.

4% of this product, dissolved in aqueous alkali, are added to a viscosespinning solution. The fibers obtained therefrom in the usual manner areoi. mat, wool-like appearance. They are easily dyed by acid wooldyestufi's, and the dyeings are oi good fastness. V

Example 5 SOaN H1 which is worked up as usual. The fibers obtainedtherefrom are well dyed by acid wool dyestufis, for instance thosementioned in Example 1. Good tone-in-tone dyeings are obtained on mixedviscose-wool material in most cases.

We claim:

1. Process for increasing the aillnity of cellu:- losic fibers towardsacid wool dyestuffs which comprises incorporating with the fibershighmolecular weight, water-insoluble. alkali-soluble sulfonamidescontaining in addition to the nitrogen of the sulfamide groups, basicnitrogen atoms.

2. Process for increasing the amnity oi artificial cellulosic fiberstowards acid wool dyestufis which comprises incorporating highmolecularweight, water-insoluble, alkali-soluble sulionamides containing inaddition to the nitrogen oi' the sulfamide groups, basic nitrogen atoms,with an alkaline cellulose solution and precipitating the fibers fromsaid solution.

3. Process for increasing the affinity or artificial cellulosic fiberstowards acid wool dyestufls which comprises incorporating highmolecularweight, water-insoluble, alkali-soluble sulfonamides containing inaddition to the nitrogen of the sulfamide groups, basic nitrogen atomswith a viscose spinning solution.

4. Cellulosic fibers having increased aflinity towards acid wooldyestuffs, said fibers having incorporated therewith high-molecularweight, water-insoluble, alkali-soluble sulfonamides containing inaddition to the nitrogen of the suitamide groups, basic nitrogen atoms.

5. Viscose artificial fibers having increased afiinity towards acid wooldyestufls, said fibers having incorporated therewith high-molecularweight, water-insoluble, alkali-soluble sulionamides containing inaddition to the nitrogen of the sulfamide groups, basic nitrogen atoms.

JOHANNES NELLES. OTTO BAYER.

